Method of producing liquid hydrocarbons and apparatus therefor



May 26, 1931. J. MARUHN ET AL METHOD OF PRODUCING LIQUID HYDROCARBONS AND APPARATUS THEREFOR Filed March 10. 1930 Y m 1 m l a 4 1 i a J b x mv u es Whiz/flaw J Wa mhh L 47a bben Patented May 26, 1931 UNITED STATES JOHANNES MARUEN, or BERLIN-FRIEDENAU, aim rmnwre BEN, F BERLIN- NICOLASSEE, GERMANY Application filed March 10, 1930, Serial No. 434,695, and in Germany 'fiecember 16, 1925.

It is known to initiate the chemical reac tion between coal, solid and liquid hydrocarbonaceous substances and hydrogen, either with or without the co-action of suitable cata- '5 lysts, under a high pressure and at a suitably high temperature by employing a plurality of apparatus, such as pumps, compressors, heating tubes, autoclaves, and the like, connected with one another in series, and to carry out the process within a shorter or longer period of time for the purpose of obtaining hydrogenation products, oils, and gases.

It is also known to obtain water-gas from liquid hydrocarbons, earth-oil, brown-coal tars and pit-coal tars, as well as thejproducts of distillation thereof, by carrying out the gasification in the interior of internal combustion-engines, the requisite'splitting process taking place during the expansion stroke, and the liquid material being introduced in the form of hydrocarbons in a manner resembling that used with Diesel motors. 7

Now, the present invention consists in the use of a suitably designed compression space of a hydraulic compression devlce, for 1nstance such as shown and described in the German patent-specification 350,619, in order' to convert in that compression space, and in one, continuous procedure carbonaceous substances, for instance fine-coal, brown-coal,

pit-coal and coke, preliminarily dried and pulverized in known manner, or heavy oils,

directly into distillable 'oils byintroducing the starting substance into said compression as space, and adding hydrogen under high pressure and at a corresponding temperature and possibly with the co-action of a substance adapted to act as a catalyst.

A hydraulic press having a suitably de- 40 signed compression space is particularly use ful for carrying out our improved method,

that is to say, for employing solid hydrocarbons or heav oils as starting materials and effecting the known hydrogenating and splitting reactions in a direct way without the insertion of special high-pressure apparatus or autoclaves into the path of the respective material.

As regards the hydrogenation of coal, this process is carried out in the manner described the reaction takes place may be uniform or hereinafter; which description is true also as regards heavy oils.

Using the compressionspace of a hydraulic press renders possible without any dificulty the working of finely pulverized coal without any addition'of oil, or turning the coal into acoal-oil-paste. There is attained in that space a' direct and intimate mixture of the substances concerned and a reaction with hydrogen which can be carried out under a high pressure that may be regulated as desired, and at a temperature of any height; catalysts may be used if desired or preferred, and the" pressure used during that period in which n variable as desired or preferred. I

- The difficulty often experienced with the known hydrogenating processes of introducing the coal in unmixed state and in solid form into the high-pressure apparatus is done away with, as the hydraulic compression device permitsthe introduction of the pulverized coal into compression space at a pressure of 1500 atm. and even higher, as is done with brown-coal briquetting machines. Besides said advantage, another advantage resides therein that, in contradistinction to all known apparatus for the hydrogenation of coal, the employment of the hydraulic press entails a considerable simplification of the process, and renders it cheaper. It must be borne in mindthat the hydraulic press presents, for initiating and carrying out the process, and above the known special highpressurecompression plants, as used hereto- S5 fore, the important technical, chemical, and economical advantages that the press we make use of-is very compact, requires, therefore, only little space, and that the requisite devices and instruments for measuring the pressure and the temperature, for admitting the substances concerned, and for regulat ing the supply thereof, can be easily watched, are easily accessible, and can likewise easily 'be exchanged, if necessary. These features 53 are the more important, as there may besulphur in the coal in spite of the conversion of the sulphur into sulphate of iron by an addition of iron oxide. Also the reduction of the volume or bulk of the material by nection with all reaction agents, reaction pressures, and reaction temperatures that have become known and have been used up to now. The object of the process per se is to obtain in a simple manner distillable oils from solid hydrocarbons in the form of sufficiently, preliminarily dried andfinely pulverized brown-coal or pit-coal, as well as fine coal, and from heavy oils.

In experimental trials in which browncoal semi-coke was used as starting material there has been obtained, for instance, an amount of distillable oil equal to from'40 to 60% in weight of that startingmaterial, from 63 to 65% of that oil boiling at 280 0., 20% at a higher temperature, and the residue amounting to 17% having a softening point of 87. Thata part of the oxygen contained in the coal is converted into water, another part is reduced to the hydroxyl group, that is to say, to phenoles, a part of the often times present sulphuris converted into hydric sulphide, a part of the nitrogen is converted into ammonia, and finally, another part is converted into gasiform hydrocarbons, all of which are knownand comprehensible phenomena which do not impair the success of the direct production of distillable oils.

The hydraulic press for carrying out our improved process is illustrated diagrammatically and by way of example on the accompanying drawing in which Figure 1 is an axial section through the press. Figure 2 is a front view ofthe same. and Figure 3 is a detail, all as fully described hereinafter;

()n the drawings, a is a cast-iron body and b a steel cylinder into which is inserted a working cylinder 0. The two cylinders can easily be removed from the body a in order to be repaired etc., if necessary. Into the cylinder 7) is cast a coil d through which hot oil is to be conducted in order to heat the reaction mass contained in the cylinders. The plunger 2 which fits into the cylinder 0 has at its inner end or face a steel cup 1' which serves as a packing and tightening member for the plunger in the cylinder 0.

This cylinder 0 is designed as a sleeve in the cylinder 6, and this latter cylinder (12) is designed as a truncated cone at its closed end and is there provided with a passage Z, as well as with a transversely located slot into which two iron ledges f (Figs. 2 and 3) can be shoved; the sectional area of the passage Z can be varied by said ledges which can be shoved towards, and away from one another and can form between them a gap of larger or smaller size, but the passage mentioned can also be completely closed by said ledges, as will be obvious in View of the particular shape of the ledges, as shown in Fig. 3. When that opening is closed, the reaction mass can be subjected to the requisite pressure which may amount to 1000 atm. and even more, and can be attained without particular pains and without any danger for the apparatus.

In the cylinder 6 is passage m and 'in the body a is a passage n, and a piece of tube 0 connects the two passages with a supply hopper p. The tube 0 is traversed by two slides h and 2' so that the material to be fed into the cylinders b and 0 can be introduced in certain individual amounts corresponding to the space between said two slides, and without bringing the interior of the cylinders in communication with the .atmosphere.

The hydrogenating gasis supplied through the pipe k which terminates in the passage 72..

If pulverulent coil is used, the operation proceeds in this way that the hydrogenated mass is compressed by the plunger e so much that space for the reception of another amount of the material and of the requisite amount of gas is provided,and the stroke. of the plunger is so determined that the new or fresh amount is compressed only after the plunger has covered and closed the orifice of the passage on so that the hydrogen is prevented from escaping through that passage.

As regards the actuation of the press, we refer to the above-mentioned German patent-specification 350,619 in which matters are fully shown and described.

We claim:

1. A method of producing lower boiling liquid hydrocarbons by hydrogenating and converting carbonaceous substances selected from a group com rising finely pulverized coal, heavy oils an mixtures of pulverized coal and oil at an increased temperature and under high pressure of hydrogen-containing gas; said method consisting in feeding to a reaction zone a mixture of hydrogen-containing gas, said carbonaceous'substances and a catalyst, heating and gradually compressing the mixture in said zone until the maximum reaction pressure is reached, and finally removing the product from said reaction zone. 2. An apparatus for producing-liquid hydrocarbons by hydrogenating carbonaceous substances selected from a group comprising finely pulverized coal, hea oils and mixtures o pulverized coal an oil at an increased temperature and high pressure with hydrogen-containing gas; comprising a heated cylinder acting as a reaction chamber and having an inlet and an outlet, a plunger ada ted to reciprocate in the bore of the cylin er, the inlet passage communieating with said bore and adapted to supply said substances and the hydrogen-containlng gas into said bore, a gate in the cylinder adapted to regulate the outlet from the cylinder, the relative position between said inlet pamage and the plunger being-such that the plunger automatically during its reciprocation acts as 'a valve for closing the inlet passage at the beginning of the stroke.

3. An apparatus for producing liquid hydrocarbons b hydrogenating carbonaceous substances seibcted from a group comprising finely pulverized coal, heavy oils and mixtures of pulverized coal and oil at an increased temperature and high pressure with hydrogen-containing as; comprising a cylinder, a coil in the b y of the c linder concentric with its axis adapted to eed hot liquid therethrough thereby heating the cylinder, a plunger adapted to reciprocate in the 5 bore of the cylinder, a hopper provided with an inlet passage communicating with said bore, means traversing said inlet passage adapted to supply the required amount of said substances passing from said hopper through the inlet passage into said bore, a

supply pipe adapted to furnish the hydrogen-containing 'gas into the inlet passa be tween said means in said bore, a gate 1n the cylinder adapted to regulate the outlet therefrom, the relative position between said inlet passage and the plunger being such that the plunger automatically during its reciprocationacts as a valve for closing the inlet pass at the beginning of the stroke. 40 fi testimony whereof we afix our signa- JOHANNES MARUHN, LUDWIG TUBBEN.

tures. 

